CN105008404B - Comprising flanking the ionomer of vinyl and preparing its method - Google Patents
Comprising flanking the ionomer of vinyl and preparing its method Download PDFInfo
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- CN105008404B CN105008404B CN201380073557.1A CN201380073557A CN105008404B CN 105008404 B CN105008404 B CN 105008404B CN 201380073557 A CN201380073557 A CN 201380073557A CN 105008404 B CN105008404 B CN 105008404B
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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Abstract
The present invention relates to ionomer, it includes a) halogenated isoolefin hydrocarbon copolymer with do not have the nucleopilic reagent for flanking vinyl b) and flank the reaction product reacted between the nucleopilic reagent of vinyl comprising at least one.The invention further relates to the methods for preparing and solidifying these ionomers.
Description
Technical field
The present invention relates to curable butyl rubber derivatives.In particular it relates to flank second comprising at least one
The ionomer of alkenyl.
Background technique
Poly- (isobutylene-co-isoprene) or IIR are that one kind is commonly known as butyl rubber (or butyl polymer)
Synthetic elastomer has passed through isobutene and a small amount of isoprene (typically no more than 2.5mol%) since the 1940's
Random cationic copolymerization prepared.Due to its molecular structure, IIR has superior air impermeability, high loss modulus, oxidation
Stability and extended fatigue resistance.
The halogenation of butyl rubber generates reactive allylic halide functionality in the elastomer.For example, Ullmann's
Encyclopedia of Industrial Chemistry (the 5th comprehensive revised edition rolls up A231, editor Elvers et al.)
And/or " Rubber Technology " (third edition) of Maurice Morton, the 10th chapter (Van Nostrand Reinhold
Company1987), in especially the 297-300 pages, the Halogenation process of conventional butyl rubber is described.
The exploitation of halogenated butyl rubber (halobutyl) is by providing much higher solidification rate and making it possible to and lead to
The serviceability of butyl is greatly extended with rubber (such as natural rubber and SBR styrene butadiene rubbers (SBR)) co-vulcanization.
Butyl rubber and halogenated butyl rubber are the polymer of high value because their unique combinations property (excellent impermeability,
Good flexible, good weatherability, co-vulcanization in the case where halogenated butyl with high degree of unsaturation rubber) make they at
For the preferred material of various applications, such as their applications in manufacture tube and tire flap.
The presence of allylic halide functionality allows nucleophilic alkylation reactions.Recently it has been proved that in the solid state, using
Nitrogen and/or Phosphorus (based on phosphorus, phosphorus based) nucleopilic reagent lead to the processing of brombutyl (BIIR)
The IIR class ionomer with interested physics and chemical property is generated (referring to Parent, J.S.；Liskova,A.；
Whitney,R.A；Resendes,R.Journal of Polymer Science,Part A:Polymer Chemistry
43,5671-5679,2005；Parent,J.S.；Liskova,A.；Resendes,R.Polymer 45,8091-8096,
2004；Parent,J.S.；Penciu,A.；Guillen-Castellanos,S.A.；Liskova,A.；Whitney,
R.A.Macromolecules 37,7477-7483,2004).The ionomer degree of functionality is by nitrogen and/or Phosphorus nucleopilic reagent
With the allyl halide site in halogenated butyl rubber react generate, to generate ammonium or phosphonium ion group respectively.
Such as other rubber, for most of applications, butyl rubber must be through compound and vulcanize (chemical crosslinking) with generation
Useful, durable final use product.The grade of butyl rubber has been developed to meet specific processing and performance requirement
And a series of molecular weight, degree of unsaturation and solidification rate.Both attribute and process equipment of final use are having in determination
It is important in the correct grade of butyl rubber used in body application.
The butyl rubber compound of peroxide-curable imparts multiple advantages relative to conventional sulfur curing system.It is typical
Ground, these compounds show very fast solidification rate and obtained cured product tends to have it is excellent heat-resisting
Property.In addition, the preparation of peroxide-curable is considered to be " completely ", because they are without containing any extractible inorganic
Impurity (for example, sulphur).Therefore, the clean rubber product can be used for such as capacitor plug (condenser cap), biology
In medical devices, pharmaceutical equipment (piston in the plug of the bottle of powder charge object, syringe) and possibly for fuel cell
In sealing element.
A kind of method for obtaining the butyl-like preparation of peroxide-curable is traditional butyl rubbers and vinyl aromatic (co)
Compounds of group (such as divinylbenzene (DVB)) and organic peroxide are applied in combination (referring to Japanese publication number 06-107738).
DVB is substituted, polyfunctional monomer (ethylene glycol dimethacrylate, trihydroxy methyl third containing electron-withdrawing group also can be used
Alkane triacrylate, N, N'- metaphenylene dimaleimide) (Japanese publication number 06-172547).
List can be used in the commercially available terpolymer XL-10000 based on isobutene (IB), isoprene (IP) and DVB
Only peroxide solidifies.But this material has the DVB of the level of signifiance.In addition, since DVB is in the course of the polymerization process
Incorporation, so the crosslinking of significant quantity has occurred during manufacture.Obtained high Mooney (Mooney) (60-75MU,
125 DEG C of ML1+8@) and existing gel particle this material is difficult to.
Canadian Patent No. 2,418,884 and Canadian Patent 2,458,741 describe the peroxide based on butyl
The preparation of the curable compound of compound, the compound have high multiolefin content.Specifically, 2 CA, 418,884 describe tool
There is the preparation of the IIR of the isoprene levels within the scope of 3-8mol%.The isoprene improved the standard in polymer backbone makes
These compounds are peroxide-curables.The halogenation of this high multiolefin butyl rubber consumes some of this degree of unsaturation
And reactive acrylic halogen functionalities are produced in the elastomer.It, can using this isoprene improved the standard
BIIR analog is generated usually to have in polymer backbone containing range in the allylic bromide functionality of 3-8mol%
There is residual double bond.As described above nucleophilic substitution can be with manufacturing ionomer portion by these allyl halide sites
Point, residual degree of unsaturation is enough to allow peroxide cure.In PCT Publication WO2007/022618 and WO2007/022619
Describe the butyl rubber ionomer composition of the peroxide-curable with high-level isoprene.
Critical failure of the elastomer compounds in dynamic application first is that crack growth.Butyl ionomer is in addition to unsaturation
Also there is ionic functionality except degree.When by these compound cures, reversible ionomer and irreversible is existed simultaneously
Chemical crosslinking.The reversible ionomer allows butyl ionomer to operate in a manner of " self-regeneration ", wherein polymerizeing
Object chain can flow to a certain extent or activity.
It therefore, is desirable with better dynamic characteristic and the butyl rubber ionomer composition of physical characteristic is shown
's.
Summary of the invention
It is an object of the present invention to provide a kind of ionomer, it includes halogenated isoolefin hydrocarbon copolymer, without flanking second
The reaction product reacted between first nucleopilic reagent of alkenyl and the second nucleopilic reagent for flanking vinyl comprising at least one.
Specific embodiment
The present invention relates to ionomer, it is used to prepare the method for these ionomers and the side for solidifying these ionomers
Method.In particular it relates to the ionomer with improved dynamic property and physical property.The butyl ionomer is by halogen
Change butyl polymer preparation.Butyl polymer is typically derived from least one isoolefin monomer, at least one multi-olefin monomer
Optionally further copolymerisable monomer.
The halogenated copolymers being used in the present invention are comprising at least one isoolefin monomer and one or more polyenoid
The copolymer of hydrocarbon monomer.
Isoalkene suitable for being used in the present invention is the hydrocarbon monomer with 4-16 carbon atom.In a reality of the invention
It applies in mode, isoalkene has 4-7 carbon atom.The example for the isoalkene being used in the present invention includes isobutene
(isobutene) (isobutene (isobutylene)), 2-methyl-1-butene alkene, 3-methyl-1-butene, 2- methyl-2-butene, 4-
Methyl-1-pentene, 4-methyl-1-pentene and mixture.Preferred isoalkene is isobutene (isobutene) (isobutene
(isobutylene))。
The polyene copolymerizable with isoalkene known to those skilled in the art can make in the practice of the invention
With.In one embodiment, multi-olefin monomer is conjugated diene.The example of such polyene includes for example with 4-14 carbon
Those of atoms range.The example of suitable polyene includes isoprene, butadiene, 2-methyl butadiene, 2,4- dimethyl
Butadiene, pepper woods alkali (piperyline, piperyline), 3- methyl-1,3- pentadiene, 2,4- hexadiene, 2- neopentyl
Butadiene, 2- methyl-1,5- hexadiene, 2,5- dimethyl -2,4- hexadiene, 2- methyl-1,4- pentadiene, 4- butyl -1,3-
Pentadiene, 2,3- dimethyl -1,3- pentadiene, 2,3- dibutyl -1,3- pentadiene, 2- ethyl -1,3- pentadiene, 2- ethyl -
1,3- butadiene, 2- methyl-1,6- heptadiene, cyclopentadiene, methyl cyclopentadiene, cyclohexadiene, 1- vinyl cyclohex diene
With their mixture.Particularly preferred conjugated diene is isoprene.
In halogenated copolymers, the one or more of repetitive unit derive from the polyene list comprising allyl halogen moiety
Body.
Can be used for that other be total to can be optionally included together with isoalkene and polyene in halogenated copolymers of the invention
Polycondensation monomer.
Comonomer includes the monomer copolymerizable with isoalkene and/or alkadienes.It is suitble to the copolymerization being used in the present invention
Monomer includes such as styrene monomer, such as alkyl-substituted vinyl aromatic comonomer, including but not limited to C1-C4Alkyl
Substituted styrene.The specific example of such comonomer includes such as α-methylstyrene, p-methylstyrene, chlorobenzene second
Alkene, cyclopentadiene and methyl cyclopentadiene.
In an embodiment of the invention, copolymer of the invention may include such as isobutene, isoprene and
The random copolymer of p-methylstyrene.
In another embodiment of the invention, make isoolefin monomer as described above and styrene monomer (such as alkane
The vinyl aromatic comonomer that base replaces, including but not limited to C1-C4Alkyl-substituted styrene) copolymerization.Styrene monomer
Specific example include such as α-methylstyrene, p-methylstyrene, chlorostyrene, cyclopentadiene and methyl cyclopentadiene.
In this embodiment, the butyl rubber polymer may include the random copolymerization of such as isobutene and p-methylstyrene
Object.
Copolymer present invention as described above is formed by the mixture of monomer described herein.In a reality
It applies in mode, the monomer mixture includes the isoolefin monomer and by weight about 1% of by weight about 80% to about 99%
To 20% multi-olefin monomer.In another embodiment, the monomer mixture includes by weight about 85% to about
99% isoolefin monomer and by weight about 1% to 15% multi-olefin monomer.In some embodiments of the present invention, may be used
To use three kinds of monomers.In these embodiments, the monomer mixture include by weight about 80% to about 99% it is different
Olefinic monomer, the multi-olefin monomer of by weight about 0.5% to about 5% and by weight about 0.5% to about 15% with it is different
Alkene or the copolymerizable Third monomer of multi-olefin monomer.In one embodiment, the monomer mixture includes by weight
The isoolefin monomer of about 85% to about 99%, the multi-olefin monomer of by weight about 0.5% to about 5% and by weight about
0.5% to 10% Third monomer copolymerizable with isoalkene or multi-olefin monomer.In yet another embodiment, the monomer
Mixture include by weight about 80% to about 99% isoolefin monomer and by weight about 1% to 20% phenylethylene list
Body.
In one embodiment, by first by the list comprising one or more isoalkene, one or more polyenes
Body mixture prepares copolymer, and obtained copolymer is then made to be subjected to halogenation process to form halogenated copolymers, thus to obtain
The halogenated copolymers.Halogenation, such as Rubber can be carried out according to well known to a person skilled in the art methods
Technology, the third edition, editor Maurice Morton, Kluwer Academic Publishers, page 297-300 with
And process described in other documents cited therein.
In one embodiment, the polyene butyl polymer includes that at least 0.5mol% derives from multi-olefin monomer
Repetitive unit.It in one embodiment, is at least 0.75mol% from the repetitive unit of multi-olefin monomer.At one
In embodiment, the repetitive unit from multi-olefin monomer is at least 1.0mol%.In one embodiment, from more
The repetitive unit of olefinic monomer is at least 1.5mol%.In one embodiment, from the repetitive unit of multi-olefin monomer
It is at least 2.0mol%.It in one embodiment, is at least 2.5mol% from the repetitive unit of multi-olefin monomer.
In one embodiment, the polyene butyl polymer includes that at least 3.0mol% derives from multi-olefin monomer
Repetitive unit.It in one embodiment, is at least 4.0mol% from the repetitive unit of multi-olefin monomer.In a reality
It applies in mode, the repetitive unit from multi-olefin monomer is at least 5.0mol%.In one embodiment, polyenoid is derived from
The repetitive unit of hydrocarbon monomer is at least 6.0mol%.In one embodiment, it is from the repetitive unit of multi-olefin monomer
At least 7.0mol%.
In an embodiment of the invention, the ionomer can be by the polyene list with 0.5-2.2mol%
The halogenated butyl rubber polymer preparation of body.For example, the halogenated butyl rubber being used in the present invention includes having isobutene
With the halogenated butyl rubber less than 2.2 moles of % isoprene, it is commercially available by LANXESS Deutschland GmbH and with
Title BB2030TMIt is sold.In yet another embodiment of the present invention, the ionomer can be by having more high multiolefin
It is prepared by the halogenated butyl rubber polymer of content (being greater than 2.5mol%).It is described from poly- in another embodiment again
Object can be by having the halogenated butyl rubber greater than 3.5mol% multi-olefin content to prepare.In yet another embodiment, described
The multi-olefin content of halogenated butyl rubber is greater than 4.0mol%.In even another embodiment, the halogenated butyl rubber
Multi-olefin content be greater than 7.0mol%.The preparation of butyl rubber polymer suitable for the high multiolefin in the present invention describes
In copending application CA 2,418,884, it is incorporated herein by reference.
During halogenation, the multi-olefin content of all or part of copolymer is converted into comprising allyl halide
Unit.These allyl halides are located in halogenated butyl polymer, generate from the original butyl polymer that is present in
The repetitive unit of multi-olefin monomer.The starting that total allylic halide content of halogen polymer does not exceed matrix copolymer is more
Olefin(e) centent.Allyl halide site allows to react with one or more nucleopilic reagents and by one or more nucleopilic reagents
It is attached to halogenated butyl polymer.
Ionomer of the invention can be by making halogenated isoolefin hydrocarbon copolymer and not having the first nucleophilic for flanking vinyl
Reagent and the reaction of the second nucleopilic reagent comprising flanking vinyl are to obtain.
It has surprisingly been found that by making halogenated isoolefin hydrocarbon copolymer with specific quantity and/or specific relative scale
The ionomer to be formed is reacted with without the nucleopilic reagent and the nucleopilic reagent comprising flanking vinyl that flank vinyl, is shown
Improved benificial physical characteristics such as anti-crack extensibility, without damaging other physical properties.
Nucleopilic reagent (with or without vinyl is flanked) suitable for preparing ionomer of the invention contains at least one
A neutral phosphor or nitrogen center with lone pair electrons, electronically be easy to participate in nucleophilic substitution on space.
In an embodiment of the invention, make the allyl halide site of halogenated copolymers of the invention and have
The nucleopilic reagent (with or without vinyl is flanked) of following basic form reacts,
Wherein,
A is nitrogen or phosphorus；And
R1、R2And R3It independently is:
Optionally comprising one or more heteroatomic linear chain or branched chain C1-C18Alkyl, C6-C10Aryl；C3-C6Heteroaryl；
C3-C6Naphthenic base；C3-C6Heterocyclylalkyl；Or their combination.
The nucleopilic reagent being used in the present invention includes the neutral nitrogen or phosphorus for for example having lone pair electrons at least one
Those of center nucleopilic reagent, they electronically be easy to participate in nucleophilic substitution on space.
Suitable includes but is not limited to diphenylphosphino styrene, allyl comprising flanking the phosphorous nucleopilic reagent of vinyl
Diphenylphosphine, diallyl Phenylphosphine, diphenylacetylene phosphine, triallyl phosphine or their mixture.
In one embodiment, the phosphorous nucleopilic reagent comprising flanking vinyl for being used in the present invention is such as
Diphenylphosphino styrene (DPPS) shown in lower.
Suitable includes but is not limited to Trimethylamine, triethylamine, three isopropyls without the nucleopilic reagent of vinyl is flanked
Base amine, three-n-butylamines, trimethyl-phosphine, triethyl phosphine, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, 2- dimethylamino
Base ethyl alcohol, 1- dimethylamino -2- propyl alcohol, 2- (isopropylamino) ethyl alcohol, 3- dimethylamino -1- propyl alcohol, N- methyl diethanol
Amine, 2- (diethylamino) ethyl alcohol, 2- dimethylamino-2- methyl-1-propyl alcohol, 2- [2- (dimethylamino) ethyoxyl] second
Alcohol, 4- (dimethylamino)-n-butyl alcohol, N- ethyldiethanolamine, triethanolamine, 3- diethylamino -1- propyl alcohol, 3- (diethyl
Base amino) -1,2- propylene glycol, 2- { [2- (dimethylamino) ethyl] methylamino } ethyl alcohol, 4- lignocaine -2- butine -1-
Alcohol, 2- (diisopropylaminoethyl) ethyl alcohol, N butyl diethanol amine, N- tertiarybutyldiethanolamine, 2- (MethYlphenylamino) ethyl alcohol, 3-
(dimethylamino) benzyl alcohol, 2- [4- (dimethylamino) phenyl] ethyl alcohol, 2- (N-ethylaniline base) ethyl alcohol, N- benzyl-N-
Methylethanolamine, N- phenyldiethanol-amine, 2- (dibutylamino) ethyl alcohol, 2- (toluidino between N- ethyl-N-) ethyl alcohol, 2,
2'- (4- methylphenylimino)-diethanol, three [2- (2- methoxy ethoxy) ethyl] amine, 3- (dibenzyl amino) -1- third
Alcohol, N- caprolactam, N- vinyl phthalimide, 9- vinyl carbazole or N- [3- (dimethylamino) third
Base] Methacrylamide and their mixture.
As described above, nucleopilic reagent is reacted with the allylic halide functionality of halogenated copolymers, ionomer part is generated
Unit, wherein the allylic halide functionality is present on halogenated copolymers.Ionomer part is in resulting ionomer
In total content do not exceed the initial amount of allyl halide in halogenated copolymers；However, it is possible to there is residual allyl halide
Compound and/or residual multiolefin.
The ratio for forming the first nucleopilic reagent used in ionomer of the invention and the second nucleopilic reagent for 4:1 extremely
100:1.In one embodiment, the ratio of the first nucleopilic reagent and the second nucleopilic reagent is 4:1 to 50:1.
In one embodiment, the ratio of the first nucleopilic reagent and the second nucleopilic reagent is 20:1.In another implementation
In mode, the ratio of the first nucleopilic reagent and the second nucleopilic reagent is 4:1.
In one embodiment, the total amount of two kinds of nucleopilic reagents used in the formation of ionomer of the invention is lower than
5phr.In another embodiment, the total amount of two kinds of nucleopilic reagents is about 1 to about 4phr.In another embodiment, two
The total amount of kind nucleopilic reagent is 2.5phr.In yet another embodiment, the total amount of two kinds of nucleopilic reagents is 2.1phr.
In one embodiment, the ratio of the first nucleopilic reagent and the second nucleopilic reagent is 20:1, and two kinds of nucleophilics
The total amount of reagent is 2.1phr.
In one embodiment, the ratio of the first nucleopilic reagent and the second nucleopilic reagent is 4:1, and two kinds of nucleopilic reagents
Total amount be 2.5phr.
In one embodiment, the copolymer simultaneously with do not have flank the nucleopilic reagent of vinyl and comprising flanking
The nucleopilic reagent of vinyl reacts.
In another embodiment, the copolymer is sequentially and without the nucleopilic reagent (first for flanking vinyl
Nucleopilic reagent) reaction, then reacted with the nucleopilic reagent (the second nucleopilic reagent) comprising flanking vinyl.In another embodiment party
In formula, such reaction can make the first and second nucleopilic reagents together by two stages react under different reaction conditions
Polymers reacts to carry out.
In an embodiment of two stages reaction, two nucleopilic reagents are in different temperature from the reaction of copolymer
And/or continue what different reaction periods carried out.
It can be in about 60 DEG C to about 200 DEG C of temperature without reacting between the nucleopilic reagent of vinyl and copolymer is flanked
Degree carries out.It in one embodiment, is about 80 without reacting between the nucleopilic reagent of vinyl and copolymer is flanked
DEG C to about 160 DEG C temperature carry out.In another embodiment, without flank vinyl nucleopilic reagent and copolymer it
Between reaction be to be carried out in about 100 DEG C to about 140 DEG C of temperature.
In one embodiment, copolymer reacts about 0.5-60 minutes with not having the nucleopilic reagent for flanking vinyl.
In another embodiment, copolymer reacts about 1-30 minutes with not having the nucleopilic reagent for flanking vinyl.At another
In embodiment, copolymer reacts about 5-15 minutes with not having the nucleopilic reagent for flanking vinyl.
It can be in about 60 DEG C to about 200 DEG C of temperature comprising flanking reacting between the nucleopilic reagent of vinyl and copolymer
It carries out.It in another embodiment, is at about 70 DEG C containing reacting between the nucleopilic reagent of vinyl and copolymer is flanked
It is carried out to about 150 DEG C of temperature.In another embodiment, containing flanking between the nucleopilic reagent of vinyl and copolymer
Reaction be to be carried out in about 80 DEG C to about 120 DEG C of temperature.In another embodiment, containing the nucleophilic for flanking vinyl
Between reagent and copolymer react be about 90 DEG C to about 100 DEG C temperature carry out.
In one embodiment, copolymer reacts about 0.5-120 minutes with the nucleopilic reagent comprising flanking vinyl.?
In another embodiment, copolymer reacts about 5-50 minutes with the nucleopilic reagent comprising flanking vinyl.In another implementation
In mode, copolymer reacts about 25-45 minutes with the nucleopilic reagent comprising flanking vinyl.
In one embodiment, copolymer with without reacting about 130 between the nucleopilic reagent for flanking vinyl
DEG C temperature carry out 10 minutes.
In one embodiment, reacting at about 90 DEG C between copolymer and the nucleopilic reagent comprising flanking vinyl
Temperature carries out 35 minutes.
Ionomer of the invention may include one or more fillers.Suitable for the filler in the present invention by of mineral
Grain composition, such as, for example, silica, silicate, clay, bentonite, vermiculite, nontronite, beidellite (beidelite), chromium
Montmorillonite (volkonskoite), hectorite, saponite, synthetic soapstone, sauconite, magadiite (magadiite),
Kenyaite (kenyaite), illite (ledikite), gypsum, aluminium oxide, titanium dioxide, talcum etc. and they
Mixture.
Other examples of suitable filler include:
Such as the high dispersibility silica prepared by the precipitating of silicate solutions or the flame hydrolysis of silicon halide,
It is with 5-1000, preferably 20-400m2The specific surface area (BET specific surface area) of/g, and the primary particle size with 10-400nm
(primary particle size)；The silica can also optionally as with other metal oxides (such as Al,
Mg, Ca, Ba, Zn, Zr and Ti) mixed oxide and exist；
Synthetic silicate, such as alumina silicate and alkaline-earth-metal silicate；
Magnesium silicate or calcium silicates, with 20-400m2The BET specific surface area of/g and the primary particle size of 10-400nm；
Natural silicate, such as kaolin and other naturally occurring silica；
Natural clay, such as montmorillonite and other naturally occurring clays；
The modified clay of organophilic substance, such as modified montmorillonite of organophilic substance (such as
It is Nanoclays, commercially available by Southern Clay Products) and modified naturally occurring viscous of other organophilic substances
Soil；
Glass fibre and glass fiber product (cushion, extrudate) or glass microsphere；
Metal oxide, such as zinc oxide, calcium oxide, magnesia and aluminium oxide；
Metal carbonate, such as magnesium carbonate, calcium carbonate and zinc carbonate；
Metal hydroxides, such as aluminium hydroxide and magnesium hydroxide or their combination.
In an embodiment of the invention, the mineral filler is silica.In another embodiment, institute
Stating mineral filler is the silica prepared by the carbon dioxide precipitates of sodium metasilicate.
The amorphous silica particles for being suitable as the drying of mineral filler according to the present invention can have place
In the average aggregate particle size (agglomerate particle size) in 1-100 micron range.Of the invention one
In a embodiment, the amorphous silica particles of the drying have the average aggregate in 10-50 micron range
Particle size.In yet another embodiment of the present invention, the amorphous silica particles of the drying, which have, is in 10-25
Average aggregate particle size in micron range.In an embodiment of the invention, it is anticipated that by volume
The aggregate particle lower than 10% is dimensionally lower than 5 microns or higher than 50 micron.Suitable amorphous dried titanium dioxide
Silicon is with such as 50-450 square metres/every gram according to DIN (Deutsche industry norm (DIN) (Deutsche Industrie Norm))
The DBP of the BET surface area of 66131 measurements and 150-400 grams/100 grams silica measured according to DIN 53601 absorbs,
The loss on drying (drying loss) of 0-10% by weight measured according to DIN ISO 787/11.Suitable titanium dioxide
Silicon filler is carried out by PPG Industries Inc. with title HiSil 210, HiSil 233 and HiSil 243 commercially available.By
Bayer AG commercially available Vulkasil S and Vulkasil N is also suitable.
Mineral filler as used in the present invention also can be used alone or be applied in combination with known Non-mineral fillers, institute
State Non-mineral fillers such as:
Carbon black；Suitable carbon black is preferably being prepared by lampblack, furnace black or channel black technique and has 20-200m2/g
BET specific surface area, such as SAF, ISAF, HAF, FEF or GPF carbon black；
Or
Rubber gels (rubber gel), are preferably based on polybutadiene, butadiene/styrene copolymers, fourth two
Alkene/those of acrylonitrile copolymer and polychlorobutadiene.
The filler of high length-diameter ratio (aspect ratio, aspect ratio) useful in the present invention includes having at least 1:3
Clay, talcum, mica of draw ratio etc..The filler may include the circle or Unequal distance material with plate or acicular texture
Material.Draw ratio is defined as the ratio of the average diameter of the circle of the same area on the surface of plate and the average thickness of plate.It is needle-shaped and
The draw ratio of bat wool is the ratio of length and diameter.In an embodiment of the invention, the filler tool of high length-diameter ratio
There is at least draw ratio of 1:5.In yet another embodiment of the present invention, the filler of high length-diameter ratio has at least major diameter of 1:7
Than.In yet another embodiment, the filler of high length-diameter ratio has the draw ratio of 1:7-1:200.Filler according to the present invention can
To have for instance in the average particle size particle size in 0.001-100 micron range.In another embodiment, filler has place
Average particle size particle size in 0.005-50 micron range.In another embodiment, filler, which has, is in 0.01-10 microns
Average particle size particle size in range.Suitable filler can have 5-200 meters squared per gram according to DIN (Deutsche industry norm (DIN))
66131 BET surface area.
In an embodiment of the invention, the filler of high length-diameter ratio includes nanoclay, such as, for example, organic change
The nanoclay of property.The present invention is not limited to specific nanoclays；But natural powdery montmorillonitic clay (such as sodium or
Calcium montmorillonite) or suitable example of the synthesis of clay (such as hydrotalcite and synthetic soapstone) as raw material.In an embodiment
In, the filler of high length-diameter ratio includes organic ester/modified montmorillonite nano clay.As known in the art, clay can pass through
Transition metal is replaced with into ion to be modified to provide the function of surfactant to clay, facilitates clay one
As dispersion in hydrophobic polymerizable substance environment.In an embodiment of the invention, ion be it is Phosphorus (for example, phosphorus from
Son) and nitrogen class (for example, ammonium ion) and containing have 2-20 carbon atom functional group (such as: NR4 +-MMT)。
The clay can be provided for example with nano-scale particle sizes, all such as less than 25 μm of volumes.Implement at one
In mode, particle size is in the range of 1-50 μm.In another embodiment, particle size is in 1-30 μm of range
It is interior.In yet another embodiment, particle size is in the range of 2-20 μm.
In addition to silicon dioxide, nanoclay can also contain the aluminium oxide of some.In one embodiment, nanometer
Clay can contain 0.1-10wt% aluminium oxide.In another embodiment, nanoclay can be aoxidized containing 0.5-5wt%
Aluminium.In yet another embodiment, nanoclay can contain 1-3wt% aluminium oxide.
It is suitable for the example packet of the commercially available organically-modified nanoclay of the filler as high length-diameter ratio in the present invention
It includes for example, with trade nameThose of clay 10A, 20A, 6A, 15A, 30B or 25A sale.In an embodiment
In, the filler of high length-diameter ratio can be added in preforming butyl rubber ionomer with the amount of 3-80phr and be answered with forming nanometer
Close object.In another embodiment, amount of the high length-diameter ratio filler in nano-complex is 5-30phr.In another implementation
In mode, amount of the high length-diameter ratio filler in nano-complex is 5-15phr.
Ionomer of the invention can be cured or uncured.It is suitble to the selection of the curing system used not special
Limitation and in those skilled in the art limit of power within.In some embodiments of the present invention, curing system can
To be based on sulphur, based on peroxide, based on resin or based on UV.
Typically the curing system based on sulphur includes: (i) metal oxide, (ii) elemental sulfur and (iii) at least one sulphur
Class promotor (accelerator, promoting agent, accelerator).Use in sulfur curing system metal oxide as component be this
It is well-known in field.Suitable metal oxide is zinc oxide, can about 1 to about 10 amount come using.In the present invention
Another embodiment in, can about 5 parts by weight of about 2- relative to 100 parts by weight butyl polymer every in nano-complex
Amount come using zinc oxide.Component (ii) elemental sulfur for including in preferred curing system is typically relative in composition every
100 parts by weight butyl polymers with the amount of about 2 parts by weight of about 0.2- come using.Suitable sulphur class promotor (preferred solidified body
Component (iii) in system) it can be relative to 100 parts by weight butyl polymer every in composition with the amount of about 0.5 to about 3 parts by weight
To use.The non-limitative example of useful sulphur class promotor can be selected from thiuram sulfide class such as tetramethyl
Thiuram (TMTD), thiocarbamate class such as zinc dimethyl dithiocarbamate (ZDC) and thiazolyl and benzo thiophene
Oxazolyl compound such as mercaptobenzothiazyl disulfide (MBTS).In an embodiment of the invention, the sulphur class promotees
It is mercaptobenzothiazyl disulfide into agent.
Curing system based on peroxide is readily applicable to use with ionomer of the invention, such as comprises more than about
The butyl rubber ionomer latex of the residual multiolefin content of 0.2mol%.For example, the curing system based on peroxide can be with
Comprising peroxide firming agent, such as dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, 2,2 '-is bis-
(t-butyl peroxy) diisopropyl benzene (40KE), benzoyl peroxide, two (tert-butyl of 2,5- dimethyl -2,5-
Peroxide)-hexin -3,2,5- dimethyl -2,5- two (benzoylperoxy) hexane, (bis- (the t-butyl peroxy) -2,5- diformazans of 2,5-
Base hexane etc..A kind of such peroxide firming agent includes dicumyl peroxide and commercially available with title DiCup 40C.
In one embodiment, the peroxide firming agent with 0.2-7 parts per hundred parts rubber (phr) amount use.
In another embodiment, the peroxide firming agent is used with the amount of 1-6phr.In yet another embodiment, described
Peroxide firming agent is used with the amount of about 4phr.
Peroxide cure auxiliary agent (co-agent) also can be used in the present invention.Suitable peroxide cure auxiliary agent
Including for example with title DIAK 7 by the commercially available triallyl isocyanurate of DuPont (TAIC) or referred to as HVA-2 (DuPont
Dow N), N '-meta-phenylene bismaleimide, triallyl cyanurate (TAC) or poly- for the liquid of Ricon D 153
Butadiene (is provided) by Ricon Resins.Peroxide cure auxiliary agent can be with the amount for being equivalent to peroxide firming agent or more
Low amount uses.Using containing the butyl polymer of degree of unsaturation of improving the standard, for example, at least multi-olefin content of 0.5mol%,
The state of the product of peroxide cure is strengthened.
In certain embodiments of the present invention, stabilizer, anti-oxidant can also be added with common amount in the usual manner
Agent, tackifier, and/or well known to a person skilled in the art other additives.
In addition it is also possible to which filler and/or other additives are added into ionomer.
In the embodiment that composition includes ionomer, filler and/or other additives, it can be used conventional compound
The ingredient is combined with each other by (being kneaded, compounding) technology.Suitable complex technique includes for example, using for example close
Mill (such as Banbury mixer), miniature internal mixer (such as Haake or Brabender mixer) or roll mill mixing machine will answer
The ingredient for closing object mixes.Extruder also provides good mixing and allows shorter incorporation time.It can carry out two
The mixing in stage or more, and the mixing can carry out in different equipment, such as a stage is in mixer
It carries out and a stage carries out in an extruder.About the further information of complex technique, referring to Encyclopedia of
Polymer Science and Engineering, volume 4, page 66 and the like (compound).Those skilled in the art
Known other technologies are also suitable for compound.
In one embodiment, it is described solidify be by the presence of peroxide firming agent in suitable solidification temperature
Degree heats what ionomer of the invention was realized.
In one embodiment, solidification temperature is about 80 DEG C to about 250 DEG C.In another embodiment, solidification temperature
Degree is about 100 to 200 DEG C.In another embodiment, solidification temperature is about 120 to 180 DEG C.
In one aspect, the present invention relates to cured polymer and product comprising as defined above and description ionomer.
Ionomer of the invention is for such as belt, sebific duct, sole, washer, o-ring, electric wire/cable, film, roller, cryptomere
The application such as object (bladder) is useful.
Illustrate the present invention now with reference to specific embodiment.It should be understood that the following example is intended to describe this
The embodiment of invention and it is not intended to be limited to the present invention anyway.
Material and reagent
Triphenylphosphine (TPP) is obtained from Alfa Aesar and uses by state when receiving.BB2030 is obtained from Sarnia
LANXESS Inc, use in storage at room temperature in dark packaging and by state when receiving.DPPS be obtained from Hokko and
It is used by state when receiving.Irganox 1010 is used purchased from Ciba and by state when receiving.Carbon black N330 be obtained from
Cabot and by receive when state use.Di-cup 40C be obtained from Struktol Canada Ltd. and by receive when
State use.HVA-2 is obtained from DuPont and uses by state when receiving.Polyethylene AC-617A is obtained from Canada
Colors and Chemicals Ltd. and by receive when state use.
The analysis of ionomer reaction
Use Bruker DRX500 spectrometer (500.13MHz1H), in CDCl3In, it is scanned using 100 times, with opposite
In the chemical shift of tetramethylsilane (TMS), pass through1H NMR analyzes rubber sample, to determine ion concentration.
Recombination process and equipment
According to following methods come composite sample:
100phr polymer [0-60 seconds]
50phr carbon black (N330) [60 seconds]
2phr polyethylene AC-617A [has carbon black]
Mixing is then poured out from mixer until about 145 DEG C (about 5 minutes).
Then in 40 DEG C of abrasive composites:
1.25phr Di-Cup 40C
1.75phr HVA-2
6 are carried out after grinding3/4Cutting and 6 longitudinal pressure refinings (endwise passes).
Introducing solidified sample in curing agent 24 hours.
Compound test equipment and program
1. equipment of table and program
Embodiment
It is prepared for following ionomer, solidifying in the presence of peroxide and evaluating them as shown in table 2A and table 2B
Physics and dynamic property.It can be clearly seen that TPP/DPPS ionomer shows the tensile strength of enhancing, omits from these tables
The tearing strength being improved and the anti-crack extensibility significantly improved.
Embodiment 1: compare
The polymer used in this comparative example is commercial LANXESS BB2030 (polymer 1).
Embodiment 2:
Triphenyl phosphorus (TPP) (2phr) is added in the BB2030 in mixer, continues 10 points in 60rpm at 130 DEG C
Clock is to form the butyl phosphorus ionomer (ionomer 1) with 0.33mol% ionic functionality.Then, using being discussed above
Process ionomer is carried out it is compound.
Embodiment 3:
TPP (2phr) is added in the BB2030 in mixer, continues 10 minutes in 60rpm at 130 DEG C to form tool
There is the butyl phosphorus ionomer of 0.33mol% ionic functionality.Then, by 0.5phr diphenylphosphino styrene in mixer
(DPPS) it is added in the ionomer, continues 35 minutes in 30rpm at 90 DEG C, obtain that there is TPPS and DPPS- ionomer
Double ionomers (ionomer 2).Then obtained ionomer is carried out using process discussed above compound.
Two stage mixing is completed for the compound containing TPP and DPPS ionomer nucleopilic reagent, it is anti-with TPP ionomer
It should be starting.
Table 2A
Table 2B
All documents quoted in a specific embodiment of the invention, relevant portion are incorporated by reference into herein；Appoint
The reference of what document is not necessarily to be construed as recognizing being the prior art for the present invention.
Although describing in detail the present invention for illustrative purposes and hereinbefore, but it is to be understood that, Ci Zhongxi
Section is only used for the purpose and those skilled in the art without departing from the spirit and scope of the present invention can be at it
In make modification, unless it is limited by claim.
Claims (34)
1. a kind of ionomer includes the reaction product reacted between the following terms:
A) halogenated isoolefin hydrocarbon copolymer, comprising the repetitive unit from least one isoolefin monomer and from a kind of or
The repetitive unit of a variety of multi-olefin monomers；With
B) do not have the first nucleopilic reagent for flanking vinyl, and flank the second nucleopilic reagent of vinyl comprising at least one；
Wherein, the ratio of first nucleopilic reagent and second nucleopilic reagent is 4:1-100:1, and is used in the reaction
Two kinds of nucleopilic reagents total amount be lower than 5phr,
And wherein include allyl halogen portion from one or more of described repetitive unit of the multi-olefin monomer
Point, the reaction occurs in allyl halogen moiety.
2. ionomer according to claim 1, wherein the ratio of first nucleopilic reagent and second nucleopilic reagent
For 4:1-50:1.
3. ionomer according to claim 1, wherein the total amount of described two nucleopilic reagents in the reactive mixture be 1 to
4phr。
4. ionomer according to claim 1, wherein the halogenated isoolefin copolymer is further included from copolymerization
The repetitive unit of monomer.
5. ionomer according to claim 4, wherein the comonomer is C1-C4The styrene that alkyl or halogen replace.
6. ionomer according to claim 1, wherein one or more multi-olefin monomers are selected from C4-C16Conjugated diene
Hydrocarbon.
7. ionomer according to claim 6, wherein the conjugated diene is isoprene.
8. ionomer described in any one of -7 according to claim 1, wherein the isoolefin monomer includes C4-C8Isomonoolefin
Monomer.
9. ionomer according to claim 8, wherein the isomonoolefin monomer includes isobutene.
10. ionomer according to claim 1, wherein the halogenated isoolefin copolymer includes halogenated butyl rubber.
11. ionomer described in any one of -7 according to claim 1, wherein not having first nucleophilic for flanking vinyl
Reagent is trimethyl-phosphine, triethyl phosphine, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine or their any mixture.
12. ionomer according to claim 11, wherein first nucleopilic reagent is triethyl phosphine.
13. ionomer described in any one of -7 according to claim 1, wherein including second nucleophilic examination for flanking vinyl
Agent is selected from by diphenylphosphino styrene, allyldiphenylphosphine, diallyl Phenylphosphine, diphenylacetylene phosphine, three allyls
The group of base phosphine and their mixture composition.
14. ionomer according to claim 13, wherein second nucleopilic reagent is diphenylphosphino styrene.
15. a kind of method for being used to prepare ionomer, comprising the following steps:
A) halogenated isoolefin hydrocarbon copolymer is provided, the halogenated isoolefin hydrocarbon copolymer includes from least one isoolefin monomer
Repetitive unit and repetitive unit from one or more multi-olefin monomers, from the described heavy of the multi-olefin monomer
One or more of multiple unit includes allyl halogen moiety；
B) the second nucleophilic examination for not having the first nucleopilic reagent for flanking vinyl and flanking vinyl comprising at least one is provided
Agent；And
React the allyl halogen moiety of the halogenated isoolefin hydrocarbon copolymer with the nucleopilic reagent described from poly- to be formed
Object；
Wherein, the ratio of first nucleopilic reagent and second nucleopilic reagent is 4:1 to 100:1, and is made in the reaction
The total amount of two kinds of nucleopilic reagents is lower than 5phr.
16. according to the method for claim 15, wherein the copolymer is sequentially reacted with first nucleopilic reagent, with
It is reacted afterwards with second nucleopilic reagent.
17. according to the method for claim 16, wherein the copolymer and first nucleopilic reagent and the second nucleophilic try
Reaction between agent carries out under different conditions.
18. according to the method for claim 15, wherein the copolymer and the first nucleopilic reagent and the second nucleopilic reagent it
Between reaction be to be carried out in different temperature.
19. according to the method for claim 16, wherein reacting between the copolymer and first nucleopilic reagent
130 DEG C of temperature carries out 10 minutes.
20. according to the method for claim 16, wherein reacting between the copolymer and second nucleopilic reagent
90 DEG C of temperature carries out 35 minutes.
21. according to the method for claim 15, wherein the halogenated isoolefin copolymer is further included from copolymerization
The repetitive unit of monomer.
22. according to the method for claim 21, wherein the comonomer is C1-C4The styrene that alkyl or halogen replace.
23. according to the method for claim 15, wherein the halogenated isoolefin copolymer includes halogenated butyl rubber.
24. method described in any one of 5-20 according to claim 1, wherein not having first nucleophilic for flanking vinyl
Reagent is trimethyl-phosphine, triethyl phosphine, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine or their any mixture.
25. method described in any one of 5-20 according to claim 1, wherein including second nucleophilic examination for flanking vinyl
Agent is selected from by diphenylphosphino styrene, allyldiphenylphosphine, diallyl Phenylphosphine, diphenylacetylene phosphine, three allyls
The group of base phosphine and their mixture composition.
26. a kind of method for being used to prepare cured polymer, comprising the following steps:
A) halogenated isoolefin hydrocarbon copolymer is provided, the halogenated isoolefin hydrocarbon copolymer includes from least one isoolefin monomer
Repetitive unit and repetitive unit from one or more multi-olefin monomers, from the described heavy of the multi-olefin monomer
One or more of multiple unit includes allyl halogen moiety；
B) the second nucleophilic examination for not having the first nucleopilic reagent for flanking vinyl and flanking vinyl comprising at least one is provided
Agent, wherein the ratio of first nucleopilic reagent and second nucleopilic reagent is 4:1 to 100:1, and two kinds of nucleopilic reagents
Total amount be lower than 5phr；
React the allyl halogen moiety of the halogenated isoolefin hydrocarbon copolymer to form ionomer with the nucleopilic reagent；With
And
D) by solidifying the ionomer in suitable solidification temperature heating.
27. according to the method for claim 26, wherein the solidification temperature is 80 DEG C to 250 DEG C.
28. according to the method for claim 26, wherein the curing schedule includes addition peroxide firming agent.
29. according to the method for claim 28, wherein the peroxide firming agent includes dicumyl peroxide, two uncles
Butylperoxide, benzoyl peroxide, 2,2 '-bis- (t-butyl peroxy) diisopropyl benzenes, 2,5- dimethyl -2,5- two
(t-butyl peroxy)-hexin -3, two (benzoylperoxy) hexane of 2,5- dimethyl -2,5- or 2,5- bis- (t-butyl peroxies) -
2,5- dimethylhexane.
30. according to the method for claim 28, wherein the peroxide firming agent is added with the amount of 0.01-7phr.
31. the method according to any one of claim 26-30, wherein the method further includes consolidating peroxide
Change auxiliary agent to mix with the peroxide firming agent and the ionomer.
32. according to the method for claim 31, wherein the auxiliary agent includes triallyl isocyanurate, N, N '-sub- benzene
Base dimaleimide, triallyl cyanurate or liquid polybutadiene.
33. a kind of product obtained by method described in any one of claim 15-23.
34. a kind of product obtained by method described in any one of claim 26-30.
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| US201261739875P | 2012-12-20 | 2012-12-20 | |
| US61/739,875 | 2012-12-20 | ||
| PCT/CA2013/001044 WO2014094121A1 (en) | 2012-12-20 | 2013-12-18 | Ionomer comprising pendant vinyl groups and processes for preparing same |
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| US (1) | US9796794B2 (en) |
| EP (1) | EP2935342B1 (en) |
| JP (1) | JP6653496B2 (en) |
| KR (1) | KR102229517B1 (en) |
| CN (1) | CN105008404B (en) |
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| EP3015521A1 (en) * | 2014-10-29 | 2016-05-04 | Lanxess Inc. | Hot melt adhesives with butyl ionomer |
| EP3231820A1 (en) * | 2016-04-15 | 2017-10-18 | ARLANXEO Canada Inc. | Polymer compositions having a halo-containing polymer with a multi-functional phosphine linkage |
| SG11202009508RA (en) * | 2018-04-03 | 2020-10-29 | Exxonmobil Chemical Patents Inc | Isobutylene-based polymers with olefinic side chain substituents and curable compositions containing the same |
| CN116003927B (en) * | 2023-03-27 | 2023-08-01 | 山东泰瑞丰新材料有限公司 | Butyl rubber capable of being repeatedly processed and preparation method thereof |
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2013
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- 2013-12-18 WO PCT/CA2013/001044 patent/WO2014094121A1/en active Application Filing
- 2013-12-18 CN CN201380073557.1A patent/CN105008404B/en active Active
- 2013-12-18 RU RU2015129316A patent/RU2654053C2/en active
- 2013-12-18 PL PL13865523T patent/PL2935342T3/en unknown
- 2013-12-18 SG SG11201504821XA patent/SG11201504821XA/en unknown
- 2013-12-18 KR KR1020157019440A patent/KR102229517B1/en active IP Right Grant
- 2013-12-18 JP JP2015548120A patent/JP6653496B2/en not_active Expired - Fee Related
- 2013-12-18 EP EP13865523.8A patent/EP2935342B1/en active Active
- 2013-12-18 US US14/653,312 patent/US9796794B2/en active Active
- 2013-12-19 TW TW102147097A patent/TW201437241A/en unknown
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2015
- 2015-06-17 SA SA515360609A patent/SA515360609B1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248134A (en) * | 2005-08-26 | 2008-08-20 | 朗盛公司 | Peroxide curable rubber compound containing high multiolefin halobutyl ionomers |
| CN101253240A (en) * | 2005-08-26 | 2008-08-27 | 朗盛公司 | Peroxide curable rubber compound containing high multiolefin halobutyl ionomers |
| CN101253241A (en) * | 2005-08-26 | 2008-08-27 | 朗盛公司 | Process for production of peroxide curable high multiolefin halobutyl ionomers |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2935342A4 (en) | 2016-06-29 |
| EP2935342A1 (en) | 2015-10-28 |
| JP6653496B2 (en) | 2020-02-26 |
| RU2015129316A (en) | 2017-01-24 |
| PL2935342T3 (en) | 2021-11-02 |
| CA2895575A1 (en) | 2014-06-26 |
| TW201437241A (en) | 2014-10-01 |
| KR102229517B1 (en) | 2021-03-18 |
| JP2016501308A (en) | 2016-01-18 |
| WO2014094121A1 (en) | 2014-06-26 |
| SG11201504821XA (en) | 2015-07-30 |
| US9796794B2 (en) | 2017-10-24 |
| SA515360609B1 (en) | 2017-03-14 |
| CN105008404A (en) | 2015-10-28 |
| RU2654053C2 (en) | 2018-05-16 |
| US20160108140A1 (en) | 2016-04-21 |
| KR20150119846A (en) | 2015-10-26 |
| EP2935342B1 (en) | 2021-03-31 |
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